JPH06136044A - Catalyst for polymerization of inner olefin and production of internal olefin polymer - Google Patents

Abstract

PURPOSE:To obtain a catalyst for polymerizing an internal olefin consisting of a product obtained by bringing a metallocene-based transition metal compound into contact with clay, etc., and an organoaluminum compound and excellent in polymerization activity. CONSTITUTION:The catalyst consists of a product obtained by bringing (A) a metallocene-based transition metal compound such as bis(cyclopentadienyl) zirconium dichloride into contact with (B) clay, clay mineral or an ion- exchangeable layer compound and (C) an organoaluminum compound such as trimethylaluminum so that molar ratio of a transition metal in the component A, hydroxyl group in the component B and aluminum in the component C may be 1/(0.5-10000)/(0.5-1000000). Furthermore, an internal olefin such as 2-butene is (co)polymerized in the presence of the catalyst to provide the objective internal olefin polymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an internal olefin polymerization catalyst and a method for obtaining an internal olefin polymer in high yield using the catalyst.

[0002]

2. Description of the Related Art In producing an olefin polymer by polymerizing an olefin in the presence of a catalyst, a method using a catalyst composed of (1) metallocene and (2) aluminoxane is proposed. (JP-A-58-019309, JP-A-2-167307, etc.).

The polymerization method using these catalysts has a very high polymerization activity per transition metal as compared with the conventional method using the Ziegler-Natta catalyst composed of a titanium compound or a vanadium compound and an organoaluminum compound, and A polymer having a narrow molecular weight distribution can be obtained. It is known that a polymer is produced also from an internal olefin by a similar catalyst (W. Kaminsky,
R. Spiehl, Makromol. Chem. 19
0,515-526 (1989)).

However, in order to obtain sufficient polymerization activity using these catalysts, a large amount of aluminoxane is required, so that the polymerization activity per aluminum is low and not only uneconomical, but also from the polymer produced. It was necessary to remove the catalyst residue. On the other hand, a method of polymerizing an olefin with a catalyst in which the above-mentioned transition metal compound and / or aluminoxane is supported on an inorganic oxide such as silica or alumina has also been proposed (JP-A-60-135408, JP-A 61-135408). 108610, 61-296008, JP-A-3-74412, and 3-74415). Further, a method of polymerizing an olefin with a catalyst in which a transition metal compound and / or an organoaluminum compound is supported on an inorganic oxide or an organic substance such as silica or alumina has been proposed (JP-A-1-101303).
JP-A 1-207303, JP-A 3-234709, JP-A 3-234710, and JP-A-3-50186.
No. 9, etc.). However, even in the methods proposed by these, the polymerization activity per aluminum is still insufficient, and the amount of the catalyst residue in the product was not negligible.

[0005]

As a result of studies to solve the above problems, the present inventors have found a catalyst having a sufficiently high polymerization activity per transition metal and per aluminum, and arrived at the present invention. That is, the present invention relates to a catalyst for internal olefin polymerization, comprising [A] a metallocene-based transition metal compound [B] clay, a clay mineral or an ion-exchange layered compound, and a product obtained by contacting [C] an organoaluminum compound. And a method for producing an internal olefin polymer, characterized by homopolymerizing or copolymerizing an internal olefin in the presence of the catalyst and, if necessary, [D] an organoaluminum compound.

The present invention will be described in detail below. An example of the metallocene-based transition metal compound used in the catalyst of the present invention, that is, the component [A] is a compound represented by the following general formula [1] or [2].

[0007]

[Chemical 1]

However, a, b, n, p, q, r and s are
It is an integer that satisfies the following formula. 0 ≦ a ≦ 5, 0 ≦ b ≦ 5, p ≧ 1, q ≧ 0, r ≧ 0 In the case of the formula [1], p + q + r = s, and in the case of the formula [2], p + q + r = s−n. .

Here, C ₅ R ¹ _a and C ₅ R ² _b represent a derivative of a cyclopentadienyl group. R ¹ and R ² are hydrogen, halogen, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing substituent, a phosphorus-containing substituent, a nitrogen-containing substituent, an alkoxy group, an aryloxy group, thio It is an alkoxy group and may be the same or different.

Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-
Butyl group, pentyl group, isopentyl group, hexyl group,
Alkyl groups such as heptyl group, octyl group, nonyl group, decyl group, phenyl group, p-tolyl group, o-tolyl group, m
-Aryl group such as tolyl group, fluoromethyl group, fluoroethyl group, fluorophenyl group, chloromethyl group, chloroethyl group, chlorophenyl group, bromomethyl group, bromoethyl group, bromophenyl group, iodomethyl group, iodoethyl group, iodophenyl group, etc. And a silicon-containing substituent such as a halo-substituted hydrocarbon group, a trimethylsilyl group, a triethylsilyl group and a triphenylsilyl group.

Further, R ¹ and R ² may be bonded to each other to form a bridging group. Specifically, methylene group, alkylene group such as ethylene group, ethylidene group, propylidene group, isopropylidene group, phenylmethylidene group, diphenylmethylidene group, and other alkylidene group, dimethylsilylene group, diethylsilylene group, dipropyl group. Silylene group, diisopropylsilylene group, diphenylsilylene group, methylethylsilylene group, methylphenylsilylene group, methylisopropylsilylene group, silicon-containing crosslinking group such as methyl-t-butylsilylene group, dimethylgermylene group, diethylgermylene group, Dipropylgermylene group, diisopropylgermylene group, diphenylgermylene group, methylethylgermylene group, methylphenylgermylene group, methylisopropylgermylene group, methyl-
germanium-containing crosslinking groups such as t-butylgermylene group,
Examples include amine and phosphine.

Further, R ^{1 s} or R ^{2 s} may be bonded to each other to form a ring. Specific examples thereof include an indenyl group, a tetrahydroindenyl group, a fluorenyl group and an octahydrofluorenyl group. R ³
Is an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, hydrogen, halogen, a silicon-containing substituent, an alkoxy group, an aryloxy group, an amide group, or a thioalkoxy group, and specifically methyl. Group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-
Butyl group, pentyl group, isopentyl group, hexyl group,
Alkyl groups such as heptyl group, octyl group, nonyl group, decyl group, phenyl group, p-tolyl group, o-tolyl group, m
-Aryl group such as tolyl group, fluoromethyl group, fluoroethyl group, fluorophenyl group, chloromethyl group, chloroethyl group, chlorophenyl group, bromomethyl group, bromoethyl group, bromophenyl group, iodomethyl group, iodoethyl group, iodophenyl group Halo-substituted hydrocarbon groups such as, halogens such as fluorine, chlorine, bromine and iodine, silicon-containing substituents such as trimethylsilyl group, triethylsilyl group and triphenylsilyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group An alkoxy group such as a butoxy group, an isobutoxy group and a t-butoxy group, a phenoxy group, a p-tolyloxy group, an m-tolyloxy group, an aryloxy group such as an o-tolyloxy group, an amide group, a dimethylamide group, a diethylamide group and a diamide group. Propylamide group, diiso Amido groups such as ropylamide group and bis (trimethylsilyl) amide group, methylthioalkoxy groups, ethylthioalkoxy groups, propylthioalkoxy groups, butylthioalkoxy groups, t-butylthioalkoxy groups, phenylthioalkoxy groups and other thioalkoxy groups can give.

R³Is R¹Or R²Combined with
As a specific example of such a ligand, C_FiveH
_Four(CH₂)_nO^-(1 ≦ n ≦ 5), C_FiveMe_Four(CH₂)_nO^-
(1 ≦ n ≦ 5), C₆H_Four(Me₂Si) (t-Bu)
N^-, C_FiveMe_Four(Me₂Si) (t-Bu) N^-Etc.
You can Furthermore, R³Bind to each other to form a bidentate ligand
You may form. R like this³As a concrete example of
^-CH₂O^-, O^-CH₂CH₂O^-, O^-(O-C₆
H _Four) O^-Etc.

M is an atom of groups 3, 4, 5, and 6 of the periodic table, and specifically, scandium, yttrium, lanthanum, cerium, praseodymium, actinium, thorium, protactinium, uranium, titanium, zirconium, Hafnium, vanadium, niobium, tantalum,
Examples include chromium, molybdenum, and tungsten. Of these, Group 4, titanium, zirconium, and hafnium are preferably used. Moreover, these may be mixed and used.

L represents an electrically neutral ligand, specifically, ethers such as diethyl ether, tetrahydrofuran, dioxane, nitriles such as acetonitrile, amides such as dimethylformamide, and trimethyl. Examples thereof include phosphines such as phosphine and amines such as trimethylamine. [R ⁴ ]
^n- is an n-valent anion, specifically, tetraphenyl borate, tetra (p-tolyl) borate, carbadodecaborate, tetrakis (pentafluorophenyl)
Examples thereof include borate, tetrafluoroborate, hexafluorophosphate and the like.

Specific examples of the compound represented by the formula [1] include bis (cyclopentadiethyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium diphenyl, and (methylcyclopenta). Dienyl) (cyclopentadienyl) zirconium dichloride, (methylcyclopentadienyl) (cyclopentadienyl) zirconium dimethyl, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium Dimethyl, (trimethylsilylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (Trimethylsillycyclopentadienyl) (cyclopentadienyl) zirconium dimethyl Bis (cyclopentadienyl) zirconium dihydride, bis (cyclopentadienyl) zirconium difluoride, bis (cyclopentadienyl) zirconium bis (trimethylsilyl), bis (cyclopentadienyl) zirconium dimethoxide, bis ( Cyclopentadienyl) zirconium diphenoxide, bis (cyclopentadienyl) zirconium bis (dimethylamide), bis (cyclopentadienyl) zirconium bis (methylthiolate), bis (cyclopentadienyl) zirconium bis (phenylthiolate) ), 3- (2,3,4,5-tetramethylcyclopentadienyl) propoxyzirconium dichloride, bis (cyclopentadienyl) zirconium-1,
2-benzenedioxide, methylenebis (cyclopentadienyl) zirconium chloride, ethylenebis (cyclopentadienyl) zirconium dichloride,
Isopropylidene bis (cyclopentadienyl) zirconium dichloride, diphenylmethylidene bis (cyclopentadienyl) zirconium dichloride, ethylene bis (indenyl) zirconium dichloride, ethylene bis (tetrahydroindenyl) zirconium dichloride, dimethylsilylene bis (cyclopentadiene) (Enyl) zirconium dichloride, dimethylsilylene bis (trimethylcyclopentadienyl) zirconium dichloride, dimethylgermylene bis (cyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (1-fluorenyl) zirconium dichloride, isopropylidene ( Cyclopentadienyl) (1-fluorenyl) zirconium dimethyl, dimethylsilylene Cyclopentadienyl) (1-
Examples thereof include fluorenyl) zirconium dichloride and cyclopentadienylzirconium trichloride.

Specific examples of the compound represented by the formula [2] include bis (cyclopentadienyl) zirconium methyltetraphenylborate, bis (cyclopentadienyl) zirconiumphenyltetraphenylborate and bis (cyclo). Pentadienyl) zirconium methyltetrakis (pentafluorophenyl) borate, bis (cyclopentadienyl) zirconium phenyltetrakis (pentafluorophenyl) borate, (methylcyclopentadienyl) (cyclopentadienyl) zirconium methyltetraphenylborate, Bis (pentamethylcyclopentadienyl) zirconium methyltetraphenylborate, bis (pentamethylcyclopentadienyl) zirconium methyltetrakis (pentafluorophenyl) bore DOO, (trimethylsilyl cyclopentadienyl) (cyclopentadienyl) zirconium methyl tetraphenylborate, 3- (2,3,4,5
Tetramethylcyclopentadienyl) propoxyzirconium methyltetraphenylborate, methylenebis (cyclopentadienyl) zirconium methyltetraphenylborate, ethylenebis (cyclopentadienyl) zirconium methyltetraphenylborate, ethylenebis (cyclopentadienyl) zirconium Methyl tetrakis (pentafluorophenyl) borate, isopropylidene bis (cyclopentadienyl) zirconium methyl tetraphenyl borate, diphenyl methylidene bis (cyclopentadienyl) zirconium methyl tetraphenyl borate, ethylene bis (indenyl) zirconium methyl tetraphenyl borate , Ethylenebis (indenyl) zirconium methyltetrakis (pentafluorophenyl) Rate, ethylenebis (tetrahydroindenyl) zirconium methyl tetraphenylborate, ethylenebis (tetrahydroindenyl) zirconium tetrakis (pentafluorophenyl) borate, dimethylsilylene bis (cyclopentadienyl) zirconium methyl tetraphenylborate,
Dimethylsilylenebis (trimethylcyclopentadienyl) zirconium methyltetraphenylborate, dimethylsilylenebis (trimethylcyclopentadienyl)
Zirconium methyl tetrakis (pentafluorophenyl) borate, isopropylidene (cyclopentadienyl) (1-fluorenyl) zirconium methyl tetraphenyl borate, isopropylidene (cyclopentadienyl) (1-fluorenyl) zirconium methyl tetrakis (pentafluorophenyl) Borate, dimethylsilylene (cyclopentadienyl) (1-fluorenyl)
Examples thereof include zirconium methyl tetraphenyl borate, cyclopentadienyl tetraphenyl borate, and tetrahydrofuran complexes of these compounds.

Further, regarding other Group 3, 4, 5, 6 metal compounds such as titanium compounds and hafnium compounds,
The compound similar to the above is mentioned. Further, a mixture of these compounds may be used. In the present invention, clay, a clay mineral, or an ion-exchange layered compound is used as the component [B]. Clay is usually composed mainly of clay minerals. Also, most clay minerals are ion-exchangeable layered compounds. The ion-exchangeable layered compound is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with each other with weak bonding forces, and the contained ions are exchangeable. Also, these clays, clay minerals,
Examples of ion-exchange layered compounds are not limited to naturally occurring compounds,
An artificial synthetic product can also be preferably used. Examples of the component [B] include clay, clay minerals, and ion-bonding compounds having a layered crystal structure such as hexagonal closest packing type, antimony type, CdCl ₂ type, and CdI ₂ type. Specific examples of the clay or clay mineral of the component [B] include cations, bentonites, kibushi clays, gyrome clays, allophanes, hissingelites, pyrophyllites, talcs, ummo groups, montmorillonite groups, vermiculites, ryokdi stones, palygorskite. , Kaolinite, nacrite, dickite, halloysite and the like. Specific examples of the ion-exchange layered compound include α
-Zr (HAsO ₄ ) ₂ · H ₂ O, α-Zr (HP
_{O 4) 2, α-Zr} (KPO 4) 2 · 3H 2 O, α-T
i (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ · H
₂ O, α-Sn (HPO ₄ ) ₂ · H ₂ O, γ-Zr (H
PO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , γ-Ti (NH
Examples include crystalline acid salts of polyvalent metals such as ₄ PO ₄ ) ₂ .H ₂ O.

The component [B] preferably has a pore volume of 20 cc or more in radius measured by mercury porosimetry of 0.1 cc / g or more, particularly 0.3 to 5 cc / g. here,
The pore volume is measured by the mercury porosimetry using a mercury porosimeter in the pore radius range of 20 to 30000Å. In this embodiment, “Aut” manufactured by Shimadzu Corporation is used.
o Pore 9200 ".

It is also preferable that the component [B] is chemically treated. Here, the chemical treatment refers to a surface treatment for removing impurities adhering to the surface or a treatment for affecting the crystal structure of clay. Specifically, acid treatment, alkali treatment,
Examples thereof include hydrochloric acid treatment and organic matter treatment. The acid treatment not only removes impurities on the surface, but also Al, Fe, M in the crystal structure.
The surface area is increased by eluting cations such as g. Alkali treatment destroys the crystal structure of clay,
It causes a change in the structure of clay. Further, in the salt treatment and the organic substance treatment, an ionic complex, a molecular complex, an organic derivative and the like can be formed to change the surface area and the interlayer distance.

By utilizing the ion exchange property, the exchangeable ion between the layers is exchanged.
Layer by replacing the ion with another large, bulky ion.
It is also possible to obtain a layered material in a state where the space is enlarged. sand
That is, bulky ions play the role of pillars that support the layered structure.
It is carried and is called a pillar. Also, between layered materials
Introducing another substance into the material is called intercalation.
U As the guest compound to be intercalated,
TiCl_Four, ZrCl _FourInorganic compounds such as T, T
i (OR)_Four, Zr (OR)_Four, PO (OR) ₃, B
(OR)₃Metal alcohol such as [R is a hydrocarbon group]
To, [Al₁₃O_Four(OH)_{twenty four}]⁷⁺, [Zr_Four(OH)₁₄]
²⁺ , [Fe₃O (OCOCH₃)₆]⁺Metal hydroxides, etc.
Ion etc. can be mentioned. These compounds used alone
Alternatively, two or more kinds may be used together. Also, this
When intercalating these compounds, Si
(OR)_Four, Al (OR)₃, Ge (OR)_FourEtc. metal
Polymer obtained by hydrolyzing alcoholate, SiO₂etc
The colloidal inorganic compound and the like can also be made to coexist.
In addition, as an example of pillars, the above-mentioned hydroxide ion is used between layers.
By intercalation and then heat dehydration
Examples include oxides produced.

The component [B] may be used as it is, or may be used after treatment such as ball milling and sieving, or may be used after newly adsorbing and adsorbing water, or after heat dehydration treatment. . Furthermore, they may be used alone or in combination of two or more of the above solids. As the component [B], clay or clay mineral is preferable, and montmorillonite is most preferable.

Examples of the organoaluminum compound used as the component [C] in the present invention include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, diethylaluminum monochloride, diethylaluminum methoxide. And the like, halogen- or alkoxy-containing alkylaluminum, aluminoxane such as methylaluminoxane, and the like, among which trialkylaluminum is particularly preferable.

Regarding the contact method for obtaining the polymerization catalyst from the components [A], [B] and [C], [A]
Transition metal in the component and hydroxyl group and [C] in the component [B]
The molar ratio of aluminum in the component organoaluminum compound is 1: 0.1 to 100,000: 0.1 to 1,000,000.
0, especially 1: 0.5-10000: 0.5
It is preferable to carry out the contact reaction at about 1,000,000.

Contact is made with pentane in an inert gas such as nitrogen.
It may be carried out in an inert hydrocarbon solvent such as hexane, heptane, toluene or xylene. The contact temperature is -20 ℃ ~
It is preferably carried out between the boiling points of the solvent, particularly preferably between room temperature and the boiling point of the solvent. Further, in the present invention, as the organoaluminum compound [D] used as necessary,
The same compounds as the component [C] can be mentioned. The amount of the organoaluminum compound used in this case depends on the catalyst component [A].
The molar ratio of the transition metal therein to the aluminum in the component [D] is selected to be 1: 0 to 10,000.

The order of contacting the catalyst components is not particularly limited. During or after the contact of each component of the catalyst, a polymer such as polyethylene or polypropylene, or a solid of an inorganic oxide such as silica or alumina may coexist or contact. The olefin may be prepolymerized in the presence of the above-mentioned components [A], [B] and [C] and optionally [D]. The prepolymerization temperature is −50 to 100 ° C., and the prepolymerization time is 0.1 to 100 hours, preferably 0.1 to 50.
It's about time.

As the organoaluminum compound which is optionally used in the prepolymerization, the same compounds as the component [C] can be mentioned. The amount of the organoaluminum compound used in this case depends on the transition metal pair [D] in the catalyst component [A].
The molar ratio of aluminum in the components is selected to be 1: 0 to 10,000. The olefin used in the prepolymerization is preferably the olefin used in the polymerization, but other olefins may be used. Also, olefins can be mixed and used.

The amount of polymer produced by prepolymerization is
It is in the range of 0.001 to 1000 g, preferably 0.1 to 300 g per 1 g of the component (B). Solvents used during prepolymerization include butane, pentane, hexane, heptane,
It is octane, cyclohexane, toluene, xylene, etc., or a mixture thereof.

The catalyst thus obtained may be used without washing or may be used after washing. When the internal olefin polymerization is carried out using the internal olefin polymerization catalyst in which the olefin is prepolymerized as described above, examples of the organoaluminum compound used as needed include the same compounds as the component [C]. The amount of the organoaluminum compound used in this case is selected so that the molar ratio of the transition metal in the catalyst component [A] to the aluminum in the organoaluminum compound is 1: 0 to 10000.

As the internal olefin which can be polymerized by the above internal olefin polymerization catalyst, 2-butene,
2-pentene, cyclopentene, cyclohexene and the like, and derivatives thereof and the like can be mentioned. Further, the polymerization can be suitably applied to not only homopolymerization but also generally known random copolymerization and block copolymerization. As the comonomer used in this case, in addition to the internal olefins as described above, commonly known α-olefins such as ethylene, propylene, 1-butene, 1-hexene, 3-methyl-1-butene, and 3-methyl are used. -1-Pentene, 4-methyl-1-pentene, vinylcycloalkane, styrene or derivatives thereof can be used. Further, a polyene such as a diene or a functional group-containing olefin such as methyl methacrylate may be allowed to coexist during the polymerization reaction.

The polymerization reaction is carried out in the presence or absence of a solvent such as an inert hydrocarbon such as butane, pentane, hexane, heptane, toluene, cyclohexane or a liquefied α-olefin. The temperature is −50 ° C. to 250 ° C., and the pressure is not particularly limited, but it is preferably atmospheric pressure to about 2000 kgf / cm ² . Further, hydrogen may be present as a molecular weight modifier in the polymerization system. Also,
The polymerization temperature and the concentration of the molecular weight modifier may be changed to carry out the polymerization in multiple stages.

[0032]

EXAMPLES Next, the present invention will be described more specifically by way of examples, but the present invention is not limited by these examples without departing from the gist thereof. Also, FIG.
Is a flowchart for facilitating the understanding of the technical contents included in the present invention, and the present invention is not restricted by the flowchart unless departing from the gist thereof.

(Example 1) (1) Synthesis of catalyst component [A] Synthesis of ethylenebisindenylzirconium dichloride The synthesis of the above complex was carried out according to the Journal of Organ.
ometallic Chemistry, 232 (19
82) 233 and the same procedure as described for ethylenebisindenyl titanium dichloride. That is, 23.2 g of commercially available indene was added to tetrahydrofuran (THF) 3
It was dissolved in 50 ml, and an n-butyllithium-hexane solution (1.6M.138 ml) was added dropwise thereto at -78 ° C. After stirring at room temperature for 4 hours, a solution of 9.5 ml of 1,2-dibromoethane dissolved in 100 ml of THF was added to -78.
Dropwise at ° C. The mixture was stirred at 50 ° C. for 12 hours. Then, 20 ml of water was added dropwise and THF was evaporated to obtain 15 g of a pale yellow solid. All the synthesis was performed under a nitrogen atmosphere.

At −78 ° C., 10 ml of the above solid and 48 ml of 1.6M butyllithium-hexane solution were added to 150 ml of THF. A red solution was obtained by stirring at room temperature for 12 hours. Separately, TH cooled to -78 ° C
To 100 ml of F was added 9.1 g of ZrCl ₄ . This solution was heated to 50 ° C., and the red solution obtained above was lowered while stirring vigorously. After stirring the mixture for 15 minutes,
It was left to cool to room temperature. After that, HCl gas was bubbled for 30 seconds to remove the solvent under reduced pressure. The solid was recrystallized from toluene to obtain 3.5 g of the orange title compound.

(2) Synthesis of catalyst Montmorillonite (Altmrich manufactured by Aldrich, Inc.) having a pore volume of 1.044 cc / g with a radius of 20 Å or more measured by a commercially available mercury intrusion method in a 100 ml round bottom flask.
Orilonite K 10) (5.20 g) was collected, and the inside of the flask was replaced with nitrogen, and then 41 ml of heptane was added to form a slurry. Separately, 1.66 g of trimethylaluminum was dissolved in 14 ml of heptane. While stirring the trimethylaluminum solution vigorously, the montmorillonite slurry was added dropwise thereto at room temperature. It generated heat with the generation of gas. After the completion of dropping, the mixture was stirred for 2 hours. Separately, 0.38 mg of the catalyst component [A] synthesized in (1) above
Was pre-contacted with 1.1 ml of a heptane solution of 402.7 mM trimethylaluminum at room temperature for 30 minutes under a nitrogen atmosphere, and further with 1.1 ml of the catalyst component slurry prepared above.

(3) Copolymerization of ethylene-cyclopentene 300 ml of toluene and the above catalyst contact mixture were introduced at room temperature under a nitrogen stream into a 2 liter induction-stirring autoclave substituted with purified nitrogen. Further, 200 ml of cyclopentene was introduced. The mixed solution was maintained at 30 ° C., ethylene was introduced so that the ethylene partial pressure was 2 kgf / cm ^2, and polymerization was carried out for 1 hour. Then, the supply of ethylene was stopped and ethanol was introduced to stop the polymerization. After that, the gas inside was purged to obtain 99.4 g of an ethylene-cyclopentene copolymer. The amount of the copolymer produced per 1 g of zirconium was 1.2 × 10 ⁶ g. Further, the amount of the copolymer produced per 1 g of aluminum derived from trimethylaluminum brought into contact with montmorillonite and the catalyst component [A] was 4018 g.

Comparative Example 1 0.38 mg of ethylenebisindenyl zirconium dichloride was used as a catalyst at room temperature under a nitrogen atmosphere in place of montmorillonite, methylaluminoxane (commercial product of Tosoh Akzo, molecular weight 123).
2; Copolymerization of ethylene-cyclopentene was carried out in the same manner as in Example 1 (3) except that the one preliminarily contacted with a toluene solution containing 4.5 mmol of Al atom was used. As a result, 59.6 g of a copolymer was obtained. Transition metal catalyst component 1 g
The amount of the produced copolymer was 7.2 × 10 ⁵ g. Moreover, the amount of propylene produced per 1 g of aluminum derived from methylaluminoxane was 491 g-polymer / g-Al.

[0038]

Industrial Applicability According to the method of the present invention, an internal olefin polymer can be obtained with an unprecedentedly high polymerization activity, and is industrially useful.

[Brief description of drawings]

FIG. 1 is a flowchart showing one embodiment of the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toru Suzuki Tohoku, Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Sanryoh Kasei Co., Ltd. Ryokasei Co., Ltd.

Claims (2)

[Claims] 1. An internal olefin polymerization characterized by comprising a product obtained by contacting [A] a metallocene-based transition metal compound [B] clay, clay mineral or an ion-exchange layered compound [C] organoaluminum compound. Catalyst. 2. A method for producing an internal olefin polymer, which comprises homopolymerizing or copolymerizing an internal olefin in the presence of the catalyst according to claim 1 and optionally [D] an organoaluminum compound.